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Publication numberUS4416873 A
Publication typeGrant
Application numberUS 06/449,117
Publication dateNov 22, 1983
Filing dateDec 13, 1982
Priority dateJun 1, 1982
Fee statusLapsed
Publication number06449117, 449117, US 4416873 A, US 4416873A, US-A-4416873, US4416873 A, US4416873A
InventorsEugene Puchalski, Frances A. Donahue, Richard P. Dixon
Original AssigneeCharles Of The Ritz Group Ltd.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Combined allantoin-hydrolyzed animal protein skin preparation
US 4416873 A
Abstract
A stable form of allantoin is provided which takes the form of a combined allantoin-hydrolyzed animal protein product which may be employed in the form of a hydroalcoholic solution, such as a cologne, after-shave lotion or skin toner, containing at least about 0.5% by weight allantoin which remains in solution, without crystallizing out, over extended periods of time.
Methods for increasing the stability of allantoin and for forming a stable form of allantoin are also provided.
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Claims(14)
What is claimed is:
1. A stable soothing hydroalcoholic skin preparation comprising a combined allantoin-hydrolyzed animal protein product in an amount of at least about 0.5% by weight, and panthenol, urea, ethanol or isopropyl alcohol and water, and optionally one or more humectants, preservatives, fragrances and solubilizing agents for the fragrances, said allantoin remaining in solution, without crystallizing out, for extended periods of time.
2. The skin preparation as defined in claim 1 wherein said allantoin and hydrolyzed animal protein are combined in the form of a complex.
3. The skin preparation as defined in claim 1 wherein said hydrolyzed animal protein is present in a weight ratio to the allantoin of within the range of from about 100:1 to about 1:1.
4. The skin preparation as defined in claim 1 in the form of an aqueous solution containing from about 0.05 to about 5% by weight allantoin and from about 0.1 to about 10% by weight hydrolyzed animal protein.
5. The skin preparation as defined in claim 4 wherein the allantoin is present in an amount within the range of from about 0.5 to about 2% and the hydrolyzed animal protein is present in an amount within the range of from about 0.1 to about 1.5%.
6. The skin preparation as defined in claim 1 wherein the hydrolyzed animal protein is a collagen-derived animal protein having a molecular weight within the range of from about 100 to about 300,000.
7. The skin preparation as defined in claim 1 wherein the panthenol is in the d- or dl-form and is present in an amount within the range of from about 0.1 to about 10% by weight.
8. The skin preparation as defined in claim 1 wherein the urea is present in an amount within the range of from about 0.1 to about 10% by weight.
9. The skin preparation as defined in claim 1 further including a preservative which is dimethyl-dimethoyl hydantoin, imidazolidinyl urea, benzyl alcohol or a paraben.
10. The skin preparation as defined in claim 1 further including a humectant which is propylene glycol, polyethylene glycols, sorbitol, glycerine, sodium-2-pyrrolidone carboxylic acid or mixtures thereof.
11. The skin preparation as defined in claim 1 further including a fragrance and a solubilizing agent for the fragrance which is polyoxyethylene (13) octyl phenyl ether.
12. The skin preparation as defined in claim 1 wherein the water is present in an amount within the range of from about 20 to about 80% by weight and the alcohol is present in an amount within the range of from about 2.5 to about 50% by weight.
13. The skin preparation as defined in claim 12 wherein the water to alcohol weight ratio is from about 1:1 to about 9:1.
14. The skin preparation as defined in claim 1 in the form of a cologne, after-shave lotion, skin toner, or emulsion.
Description

This is a continuation of application Ser. No. 383,404, filed June 1, 1982, now U.S. Pat. No. 4,374,766, issued Feb. 22, 1983.

FIELD OF THE INVENTION

The present invention relates to a stable form of allantoin which may be used in various skin preparations and other products in amounts of at least about 0.5% by weight allantoin, without crystallizing out of solution, and to methods for increasing the stability and solubility of allantoin in hydroalcoholic solutions.

BACKGROUND OF THE INVENTION

Allantoin (glyoxyl diureide) and derivatives thereof such as ALPANTHA (Schuylkill Chemical Co., Philadelphia, Pa. trademark for "Allantoin DL-Panthenol Modified") are known for their soothing, skin softening and healing activity and have been used in 0.2% concentrations in creams, lotions, lipsticks, hair products (anti-dandruff), cosmetic gels (for their anti-irritant) properties), cleansers (removal of scaly and calloused tissue), and moisturizers (increase water-binding capacity of the tissues).

Until now, notwithstanding the acknowledged therapeutic qualities of allantoin and its derivatives including allantoin dl-panthenol modified, the amount of allantoin or allantoin equivalent contained in these materials and employed in hydroalcoholic solutions (also referred to as aqueous-alcoholic solutions), such as after-shave lotions and colognes, has been severely restricted to relatively small amounts of 0.2% by weight or less. It has been found that when amounts of allantoin or allantoin dl-panthenol (modified) of greater than 0.25% by weight (based on the amount of allantoin) are employed in such hydroalcoholic solutions, the allantoin tends to crystallize out of solution within a relatively short period of time.

Accordingly, a long felt want exists in the market place for a stable form of allantoin which may be used in solution in amounts greater than 0.25% (based on the weight of allantoin) and upwards of 0.5% and more without crystallizing out of solution.

DESCRIPTION OF THE INVENTION

In accordance with the present invention, a complex or otherwise combined mixture of allantoin and hydrolyzed animal protein is provided which affords allantoin in a form which is easily solubilized in aqueous-alcoholic solutions in amounts of from about 0.05% up to about 5% and preferably from about 0.5 to about 2% based on the weight of allantoin. Such solutions may take the form of stable soothing hydroalcoholic skin preparations, such as colognes, after-shave lotions, skin toners, after bath splash and the like. The allantoin in the form of its complex or otherwise combined state, such as hydrogen bonding, with the hydrolyzed animal protein, will remain fully dissolved in the solution, without forming crystals, over extended periods of time.

The complex or otherwise combined allantoin and hydrolyzed animal protein product of the invention will contain the hydrolyzed animal protein in a weight ratio to the allantoin of within the range of from about 100:1 to about 1:1, preferably from about 5:1 to about 1:1, and optimally about 1:1.

In another aspect of the present invention, a method is provided for preparing the complex of the invention, which method includes the steps of mixing allantoin and hydrolyzed animal protein in aqueous medium at a temperature of from about 45 to about 80 C., preferably from about 55 to about 75 C., and more preferably from about 60 to about 65 C., for a period of from a few minutes (for example, 10 to 15 minutes) up to 11/2 hours or more to form a clear aqueous solution containing the complex. The clear aqueous solution will contain from about 0.05 to about 5% and preferably from about 0.5 to about 2% allantoin, and from about 0.1 to about 10% and preferably from about 0.1 to about 1.5% hydrolyzed animal protein.

The clear solution comprising the product of the invention may be used as such in the formation of any of the skin preparations mentioned or other products. If desired, the clear solution containing the complex of the invention may be dried, for example, freeze dried (or lyophilized) to form the complex or otherwise combined allantoin-hydrolyzed animal protein product in the form of a dry powder which may be subsequently added to water to form a solution or just simply added as a solid to powders, such as body and foot powders, emulsions, shampoos, acne products and the like.

The term "hydrolyzed animal protein" as employed herein refers to hydrolyzed collagen-derived animal protein having a molecular weight of within the range of from about 100 to about 200,000 and containing various amino acids including glycine, alanine, serine, threonine, proline, hydroxyproline, valine, isoleucine, phenylalanine, tyrosine, cystine/cysteine, methionine, aspartic acid, glutamic acid, arginine, histidine, lysine and hydroxylysine. Among the preferred hydrolyzed animal protein materials suitable for use herein are the collagen hydrolysates and derivatives referred to by the trademark CROTEINS manufactured by Croda, Inc., N.Y.C., Umordant sold by Pentapharm, Inc., Super-Pro 100 sold by Stepan Chemical Co., Proto-Lan 20 sold by Maybrook Inc., Lexein X-250 sold by Inolex Corp., Lanasan CL sold by Sandoz, Inc. and Peptein 2000 sold by Hormel. The Croda product is formed by hydrolyzing collagen (by alkali, acid or enzyme hydrolysis) and breaking the long collagen chains so that the molecular weight is reduced from the millions to hydrocolloids ranging from a molecular weight of 100 to 300,000 and preferably from 100 to 200,000. Amino acid composition of preferred collagen derived protein is set out below.

______________________________________Amino Acid      % Present______________________________________Glycine         20.0-30.5Alanine         8.0-11.0Serine          2.9-4.1Threonine       1.8-2.6Proline         13.7-18.0Hydroxyproline  12.1-14.5Valine          2.1-3.4Isoleucine      1.3-1.8Leucine         2.8-3.5Phenylalanine   1.1-2.6Tyrosine        0.2-1.0Cystine/Cysteine           0.0-0.9Methionine      0.7-0.9Aspartic Acid   5.7-9.0Glutamic Acid   10.0-11.7Arginine        7.8-9.0Histidine       0.7-1.0Lysine          3.9-5.2Hydroxylysine   0.7-1.2______________________________________

As indicated, the combined allantoin-hydrolyzed animal protein product of the invention may be employed in a wide variety of products. A preferred product is a stable soothing skin preparation which contains from about 0.5 to about 15% and preferably from about 0.5 to about 7% by weight of the complex or combined allantoin-hydrolyzed animal protein product. The stable soothing skin preparation also contains panthenol, which serves as a skin moisturizer and humectant and is converted to an essential vitamin B-5 for the normal growth and toning of the tissue, present in an amount within the range of from about 0.1 to about 10% by weight, and preferably from about 0.1 to about 3% by weight; and urea, which functions as a skin conditioner, water-binding agent or skin softener present in an amount within the range of from about 0.1 to about 10%, and preferably from about 0.1 to about 5% by weight.

The above skin preparation will be in the form of an aqueous-alcoholic solution and as such will contain ethanol or isopropyl alcohol in an amount within the range of from about 2.5 to about 70%, and preferably from about 10 to about 30% by weight, and water in an amount within the range of from about 20 to about 80%, and preferably from about 40 to about 75% by weight. Thus, the aqueous-alcoholic solution will contain a weight ratio of water to alcohol of within the range of from about 9:1 to about 1:1, and preferably from about 4:1 to about 1:1.

The hydroalcoholic skin preparation of the invention may contain amounts of allantoin (greater than 0.5%) heretofore never retained in solution for extended periods of time. This apparently has been achieved by employing the allantoin in combined form with the hydrolyzed animal protein. It is theorized that the allantoin forms a complex with hydrolyzed animal protein which complex is substantially more soluble in the hydroalcoholic solution than is the allantoin by itself and so remains in solution for indeterminate periods. The result is that large amounts of allantoin (greater than 0.5%) may be employed to provide even more skin soothing preparations which remain stable over extended periods of time without having the allantoin crystallize out.

The stable soothing skin preparation containing the combined allantoin-hydrolyzed animal protein product may also comprise colognes, after-shave lotions, skin toners, emulsions, powders and the like. Accordingly, such skin preparations may include preservatives, examples of which include dimethyldimethoyl hydantoin, benzyl alcohol, imidazolidinyl urea, parabens and the like usually employed in amounts within the range of from about 0.05 to about 1.25% by weight, humectants, such as, sodium 2-pyrrolidone carboxylic acid, sorbitol, polyethylene glycols, propylene glycol, glycerine or other known humectants usually employed in amounts within the range of from about 0.1 to about 20% by weight, fragrances in amounts within the range of from 0 to about 35%, and preferably from about 0.1 to about 20% by weight depending upon the ultimate use of the skin preparation; and solubilizing agents and emulsifiers for the fragrances, such as polyoxyethylene (13) octyl phenyl ether and polyoxyethylene (26) glycerine (for feel and lubricating) and other skin softeners, such as esters, lanolin, lanolin derivatives thereof and/or other conventional skin softeners, present in an amount within the range of from about 0.1 to about 10% by weight, and color as deemed necessary.

The skin preparation may also include therapeutic agents, such as benzoyl peroxide, methyl salicylate or sun-screens in amounts normally employed for the particular therapeutic agent present.

Preferred formulations within the scope of the present invention contain from about 0.6 to about 3.5% by weight combined allantoin-collagen-derived animal protein, from about 0.1 to about 3% by weight d- or dl-panthenol, from about 0.1 to about 5% by weight urea, preservatives, such as benzyl alcohol, imidazolidinyl urea and/or dimethyldimethoyl hydantoin, humectants such as sodium-2-pyrrolidone carboxylic acid, emulsifiers, such as polyoxyethylene (13) octyl phenyl ether, feel enhancers, such as polyoxyethylene (26) glycerine, fragrance, water and ethanol or isopropyl alcohol.

The skin preparations containing the combined allantoin-hydrolyzed animal protein product may be prepared as follows.

Ethanol or isopropyl alcohol, and where present, preservatives such as benzyl alcohol, fragrance oils, and emulsifiers and solubilizing agents for the fragrance oils are mixed together to form a first mixture.

Allantoin, hydrolyzed animal protein, d- or dl-panthenol, urea, and, where present, humectants, preservatives such as dimethyldimethoyl hydantoin and water are mixed together to form a second mixture containing the allantoin-hydrolyzed animal protein combined product. The second mixture is heated to about 60 to 65 C. or until clear, and then cooled to about 25 C.

The second mixture is added to the first mixture with agitation and the mixture is allowed to age for 2 to 4 days. The mixture is then chilled at 0 to 4 C., filtered and coloring solution is added to form the skin preparation of the invention.

The following Examples represent preferred embodiments of the invention.

EXAMPLE 1

A combined allantoin-hydrolyzed animal protein product in accordance with the invention was prepared as described below.

0.5 Grams allantoin and 0.5 gm hydrolyzed animal protein (Crotein SPA) are mixed with 66 gm of water and the mixture was heated at 60 to 65 C. for about 10 minutes until a clear solution forms. The mixture is then allowed to cool to room temperature and is then ready for use as an additive in colognes, after-shave lotions, skin toners, shampoos, acne products, emulsions, and the like.

If desired, the above solution may be freeze-dried to form a concentrate or powder comprising the combined allantoin-hydrolyzed animal protein which may be used in powder compositions such as body and foot powders, various cosmetics, and the like.

EXAMPLE 2

A stable soothing cologne having the following composition was prepared as described below.

______________________________________Ingredient            Parts by Weight______________________________________Mix AEthanol (denatured alcohol                 20SDA 40 Reg)Benzyl alcohol        0.5Polyoxyethylene (13) octyl                 7phenyl ether (TRITON X-102)Polyoxyethylene (26) glycerine                 0.5(LIPONIC EG-1)Fragrance             3.3Mix BAllantoin             0.5Hydrolyzed animal protein                 0.5(Crotein SPA)dl-Panthenol          1Na-2-pyrolidone carboxylic acid                 0.2(AJIDEW-N--50)Urea                  0.5Dimethyldimethoyl hydantoin (55%)                 0.2(Glydant)Deionized water       66Color (FD&C Blue #1 - 0.20.1% aqueous solution)______________________________________

The ingredients identified by Mix A were mixed together to form a first mixture. The ingredients identified by Mix B were mixed together to form a second mixture which was heated to 60-65 C. until a clear solution formed and then cooled to room temperature. The first mixture was then added to the second mixture (containing the combined allantoin-hydrolyzed animal protein product) with stirring and the combined mixture was then chilled to 0-4 C., and filtered through a #7 Ertel pad. The color solution was then added to form the soothing cologne of the invention wherein the allantoin remained stable and in solution, without crystallizing out, over extended periods of several months.

EXAMPLE 3

A stable soothing after-shave lotion having the following composition was prepared as described in Example 1.

______________________________________Ingredient           Parts by Weight______________________________________Mix AEthanol (denatured alcohol                20SDA 40 Reg)Benzyl alcohol       0.5Polyoxyethylene (13) octyl phenyl                4ether (TRITON X-102)Polyoxyethylene (26) glycerine                0.3(LIPONIC EG-1)Fragrance            2______________________________________

______________________________________Ingredient            Parts by Weight______________________________________Mix BAllantoin             0.5Hydrolyzed animal protein                 0.5(Crotein SPA)dl-Panthenol          1Na-2-pyrrolidone-5-carboxylate                 0.5(AJIDEW-N--50)Urea                  0.5Dimethyldimethoyl hydantoin (55%)                 0.2(Glydant)             70Deionized waterFD&C Blue #1 (0.1% aqueous                 0.1solution)______________________________________

The after-shave lotion produced as described above was found to have excellent stability with the allantoin remaining in solution, without crystallizing out, over extended periods of time.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2303765 *Sep 14, 1940Dec 1, 1942Claude R WickardPreparation of ammonium allantoinate
US4374766 *Jun 1, 1982Feb 22, 1983Charles Of The Ritz Group Ltd.Combined allantoin-hydrolyzed animal protein product and method
Non-Patent Citations
Reference
1 *`Allantoin`, Brochures I and II, Schuylkil Chemical Co., Philadelphia, PA.
2 *Croda 77-Crotein Specifications Sheets, pp. 23-24.
3 *DL-Panthenol-Product Data, Roche.
4 *Proteins in Cosmetics & Toiletries, Johnson, D & CL, Jun. 1980, pp. 36-38.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4883654 *Oct 6, 1988Nov 28, 1989Young Deborah ACosmetic preparation
US4942153 *Feb 3, 1987Jul 17, 1990Fernandez Helen MSkin moisturizing product and process
US4963350 *Jun 16, 1989Oct 16, 1990Goldstein Samuel ALiquid shaving product
US4973473 *Jun 23, 1989Nov 27, 1990Revlon, Inc.Skin care preparation
US5622693 *Apr 28, 1995Apr 22, 1997Shiseido Company Ltd.Solid cosmetic composition
US5711823 *Feb 21, 1995Jan 27, 1998Wilmington Partners L.P.Method for wetting contact lenses
US5872086 *Sep 17, 1997Feb 16, 1999Wilmington Partners LpComposition for wetting contact lenses
US6017517 *Dec 3, 1997Jan 25, 2000The Dial CorporationMethod for treating human nails
US7060260 *Feb 4, 2004Jun 13, 2006E.I. Du Pont De Nemours And CompanyWater-soluble silk proteins in compositions for skin care, hair care or hair coloring
US7220405Sep 7, 2004May 22, 2007E. I. Du Pont De Nemours And CompanyPeptide-based conditioners and colorants for hair, skin, and nails
US7285264Mar 27, 2006Oct 23, 2007E.I. Du Pont De Nemours And CompanyPeptide-based body surface coloring reagents
US7390431Mar 10, 2006Jun 24, 2008Jr Chem, LlcStable organic peroxide compositions
US7445729Nov 21, 2007Nov 4, 2008Jr Chem, LlcStable organic peroxide compositions
US7544353Mar 9, 2007Jun 9, 2009E.I. Du Pont De Nemours And CompanyPeptide-based conditioners and colorants for hair, skin, and nails
US7556820Nov 4, 2008Jul 7, 2009Jr Chem, LlcStable organic peroxide compositions
US7560119Jun 23, 2008Jul 14, 2009Jr Chem, LlcStable organic peroxide compositions
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US7691829Mar 4, 2005Apr 6, 2010Petito George DComposition and method for healing tissues
US7700716Dec 1, 2006Apr 20, 2010E. I. Du Pont De Nemours And CompanyPolytetrafluoroethylene binding peptides and methods of use
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US7807141Jan 10, 2008Oct 5, 2010E.I. Du Pont De Nemours And CompanyPeptide-based oral care surface reagents for personal care
US7858581Dec 1, 2006Dec 28, 2010E. I. Du Pont De Nemours And CompanyPMMA binding peptides and methods of use
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US7964180Apr 6, 2010Jun 21, 2011E. I. Du Pont De Nemours And CompanyMethod for enhancing effects of colorants and conditioners
US8168599Mar 16, 2010May 1, 2012Petito George DComposition and method for healing tissues
US8475772Aug 10, 2010Jul 2, 2013E I Du Pont De Nemours And CompanyPeptide-based oral care surface reagents for personal care
EP2016934A1Mar 8, 2005Jan 21, 2009E. I. Du Pont de Nemours and CompanyPeptide-based body surface reagents for personal care
EP2374465A1Sep 8, 2004Oct 12, 2011E. I. du Pont de Nemours and CompanyPeptide-based conditioners and colorants for hair, skin and nails
WO2006099187A2 *Mar 10, 2006Sep 21, 2006Joseph R FaryniarzBenzoyl peroxide compositions and methods of use
WO2011018540A2Jul 30, 2010Feb 17, 2011Prieto Alonso Jose AndresLiquid shaving preparation
Classifications
U.S. Classification514/18.6, 530/356, 530/407, 530/300, 424/63, 424/69, 424/70.14, 424/73, 514/21.92
International ClassificationA61K8/65, A61Q19/00, A23J3/00, C07D233/88, A61K8/49
Cooperative ClassificationA61K8/65, A61Q19/00, A23J3/04, A61K8/4946, A61Q19/002, C07D233/88
European ClassificationA61K8/49F1, A61K8/65, A23J3/04, A61Q19/00, C07D233/88
Legal Events
DateCodeEventDescription
Feb 4, 1992FPExpired due to failure to pay maintenance fee
Effective date: 19911124
Nov 24, 1991LAPSLapse for failure to pay maintenance fees
Jun 25, 1991REMIMaintenance fee reminder mailed
Feb 20, 1990ASAssignment
Owner name: CRG-YSL INC.
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Effective date: 19870804
Owner name: YVES SAINT LAURENT PARFUMS CORP.
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Effective date: 19871229
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Owner name: CHARLES OF THE RITZ GROUP LTD., FORMERLY KNOWN AS
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Effective date: 19870804
Owner name: CRG HOLDING INC.
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Effective date: 19870821
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CRG HOLDINGS INC.;REEL/FRAME:004761/0983
Owner name: CHARLES OF THE RITZ GROUP LTD., FORMERLY KNOWN AS
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Effective date: 19870804
Apr 27, 1987FPAYFee payment
Year of fee payment: 4
Jan 31, 1984CCCertificate of correction